Durable coating compositions containing novel aspartic amine compounds

ABSTRACT

A coating composition comprising a binder of
         a. polyisocyanate crosslinking agent;   b. an isocyanate-reactive component having at least one compound having the following formula (I) including isomers and mixtures of isomers thereof:       

     
       
         
         
             
             
         
       
         
         
           
             wherein 
             R, R 1 , R 2 , X, Y, Z, m, n, p, q, r and s are described in the specification and a two component composition formulated with the above constituents and substrates, such as, automotive and truck bodies and parts coated with the novel composition and novel amine and/or hydroxy amine compounds are also part of the invention.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional Application Ser.No. 60/636,350 filed on Dec. 14, 2004 which are hereby incorporated byreferences in its entirely.

FIELD OF THE INVENTION

This invention is directed to coating compositions, in particular, tocoating compositions that are useful as exterior clear finishes forautomobiles and trucks.

DESCRIPTION OF THE PRIOR ART

The finishing system of choice presently being used on the exterior ofautomobiles and trucks comprises a clear coating applied over pigmentedbase coating that is applied over a primer coating. The clear coatingprovides protection, in particular, protection from weathering, to thepigmented base coating and improves the appearance of the overallfinish, in particular, provides improved gloss and distinctness ofimage. The primer coating provides adhesion to the substrate and, inparticular, provides resistance to stone chipping. When used inrefinishing of automobile and truck bodies, the clear coating and primercoating are required to have an acceptable “pot life” and reasonablyshort cure time period to allow for application of a subsequent coat andin the case of a clear coating to allow for further processing orhandling of the vehicle without damaging the finish. The term “pot life”means the period of time after a coating is mixed with a crosslinkingagent, with or without a catalyst, in which the composition remains at asprayable viscosity.

The following U.S. Pat. Nos. 5,516,873, 5,126,170, 5,243,012, 5,236,741,5,412,056, 5,580,945, and 6,005,062, show a variety of coatingcomposition that contain polyaspartic acid derivatives but thesecompositions do not have a property balance of acceptable pot life andrapid curing time to form a sufficiently hard finish to allow additionalhandling and processing of a coated vehicle or work piece after thecoating composition has been applied.

To improve the rate of curing EP 0939091 uses reactive amine compounds.A typical example of such an amine is the reaction product of4,4′-methylenebiscyclohexanamine with two moles of diethyl maleate.However, coating compositions formulated with these reactive amines donot have the desired balance of acceptable pot-life and the desired curerate after application to an object while maintaining or improving onthe desired properties of the resulting finish. In an effort to improvepot life, solvents and catalysts have been used but solvents have adeleterious effect on VOC (volatile organic content) emissions, which isundesirable and catalysts can result in deterioration of filmproperties, such as durability. It is, therefore, desired to find aclass of amine functional compounds for the reaction with isocyanates,which form coating compositions that overcome these problems and formacceptable finishes for automotive and truck substrates.

The novel composition of this invention utilizes amine and hydroxy aminefunctional compounds that form low VOC coating compositions having anoptimum balance of pot life and curing time and form finishes, inparticular, clear and primer finishes useful for automobiles and trucks.The clear coatings have excellent properties, such as hardness, gloss,low color, durability, weatherability, and in particular resistance toUV (ultraviolet light) degradation, particularly when reinforced withultraviolet light absorbers and screeners and hindered amine lightstabilizers. The primer coatings exhibit excellent adhesion to metalsubstrates, in particular, aluminum and steel substrates, and providefor excellent stone chip resistance.

SUMMARY OF THE INVENTION

A coating composition comprising a binder of

a. polyisocyanate crosslinking agent;

b. an isocyanate-reactive component having at least one compound havingthe following formula (I) including isomers and mixtures of isomersthereof:

wherein

R is a hydrocarbon radical obtained by removing (m+n) hydrogen atomsfrom a C₁ to C₂₀ linear or branched alkyl group, or a C₅ to C₁₆cycloaliphatic group; alternatively, R is a residue obtained by removingn amino groups from a polyether polyamine with m equal to 0 having afunctionality of n and a number average molecular weight of less than600, wherein the amino groups are attached to primary carbon atoms andthe ether groups are separated by at least two carbon atoms;

m equals 0 to 4, and m preferably equals 0, 1 or 2, and n, on average,equals 1 to 4, and preferably, n, on average, equals 1 and 2, with theproviso that m cannot be 0 unless n equals at least 2 if r equals 0 andZ does not contain an OH-group, n equals 1 and r equals 1 and Z does ordoes not contain an OH-group, or n equals 1, r equals 0 and Z containsat least one OH-group;

X and Y each independently can be O or NR³;

R³ is H, or C₁ to C₂₀ linear or branched alkyl group, a C₅ to C₁₆cycloaliphatic group, or R³ is equal to C₃═O if s=0, i.e. the compoundis a cyclic imide;

Z is selected from a C₁ to C₂₀ linear or branched alkyl group, a C₅ toC₁₆ cycloaliphatic group, or an OH-group containing linear, branched orcycloaliphatic alkyl group, preferred groups for Z are methyl, propyl,n-butyl, iso-butyl, sec-butyl, tert-butyl, or cyclohexyl; or Z comprisesa fragment of the structure —CH₂—CHR⁴—R⁵, with R⁴ equal to H, or C₁ toC₂₀ linear or branched alkyl group, or a C₅ to C₁₆ cycloaliphatic groupand R⁵ equal to —CN or —C(═O)OR⁶, with R⁶ equal to H, or C₁ to C₂₀linear or branched alkyl group, or a C₅ to C₁₆ cycloaliphatic group;

p and q are equal to 0 or 1, if p and q equal to 1, the —NH—Z fragmentcan be bound to either C₁ or C₂, and mixtures of compounds and isomersare commonly utilized by this invention;

s is equal to 0 or 1, with the proviso that s can only be 0 if p equals1 and X═NR³ wherein R³ equals C₃═O (cyclic imide);

R² is H or independently selected from a C₁ to C₂₀ linear or branchedalkyl group, or a C₅ to C₁₆ cycloaliphatic group;

R¹ is a hydrocarbon radical obtained by removing (q+r) hydrogen atomsfrom a C₁ to C₂₀ linear or branched alkyl group, or a C₅ to C₁₆cycloaliphatic group; and

r is equal to 0 to 4, and r preferably, equal to 0 or 1.

Two component composition formulated with the above constituents,substrates, such as, automotive and truck bodies and parts coated withthe novel composition and novel amine and/or hydroxy amine compounds arealso part of this invention.

DETAILED DESCRIPTION OF THE INVENTION

The features and advantages of the present invention will be morereadily understood, by those of ordinary skill in the art, from readingthe following detailed description. It is to be appreciated thosecertain features of the invention, which are, for clarity, describedabove and below in the context of separate embodiments, may also beprovided in combination in a single embodiment. Conversely, variousfeatures of the invention that are, for brevity, described in thecontext of a single embodiment, may also be provided separately or inany sub-combination. In addition, references in the singular may alsoinclude the plural (for example, “a” and “an” may refer to one, or oneor more) unless the context specifically states otherwise.

The use of numerical values in the various ranges specified in thisapplication, unless expressly indicated otherwise, are stated asapproximations as though the minimum and maximum values within thestated ranges were both preceded by the word “about.” In this manner,slight variations above and below the stated ranges can be used toachieve substantially the same results as values within the ranges.Also, the disclosure of these ranges is intended as a continuous rangeincluding every value between the minimum and maximum values.

All patents, patent applications and publications referred to herein areincorporated by reference in their entirety.

A typical auto or truck body is produced from a steel sheet or a plasticor a composite substrate. For example, the fenders may be of plastic ora composite and the main portion of the body of steel. If steel is used,it is first treated with an inorganic rust-proofing compound, such as,zinc or iron phosphate and then a primer coating is applied generally byelectrodeposition. Typically, these electrodeposition primers areepoxy-modified resins crosslinked with a polyisocyanate and are appliedby a cathodic electrodeposition process. Optionally, a primer can beapplied over the electrodeposited primer, usually by spraying, toprovide better appearance of a base coating or a mono coating appliedover the primer and to improve the adhesion of such coatings to theprimer or both of the above. A mono coating of a pigmented coatingcomposition then can be applied but preferably, a pigmented base coatingwith a clear top coating is applied to form a clear coat/color coatfinish on the truck or automobile body or auto or truck part. Usually,after application, each of the coatings may be cured at ambienttemperature or by baking at an elevated temperature. It is generallyknown that a clear top coating can be applied over the base coating andboth coatings cured together at an elevated temperature.

When refinishing automobile and truck bodies, the original OEM topcoatis usually sanded and a primer or sealer coat applied and then a monocoat or a basecoat/clear coat is applied. These coatings are usuallycured at ambient temperatures or at slightly elevated temperatures, suchas, 40 to 100° C.

A “clear coating composition” for automotive use is a composition thatforms a transparent finish upon curing and typically has a DOI(distinctness of image) of more than 70 and a 20°gloss of more than 70.These clear coatings provide a glossy in depth appearance to the finishon the automobile or truck and therefore, are required to have goodgloss and distinctness of image. Also, the clear finish also provides aprotective finish that is durable and resistant to scratching, marringand chipping and also provides resistance to weathering, in particularto U.V. degradation and photo-oxidation.

A “matte clear coating composition” can also be used, for example forthe interior of an automobile or truck. These matte finishes have asubstantially lower gloss, for example, a 20°gloss of 20 or less andvery low DOI.

Typical “primer compositions” provide adhesion to a substrate and forthe novel compositions of this invention provide excellent adhesion tobare metal substrates, such as, steel and aluminum, and to treated metalsubstrates, such as galvanized steel, and provide a surface to which thetopcoat, such as, a pigmented mono coat or the basecoat of a base coatclear coat finish.

The term “binder” as used herein refers to the film forming constituentsof the composition that include the isocyanate reactive component, i.e.,having functional groups that are reactive with isocyanates andcomprising active hydrogen, and optional polymeric and/or oligomericcomponents, polyisocyanate crosslinking agents and optional reactivediluents, such as, ketimines and aldimines and optional acrylicnon-aqueous dispersions. Solvents, pigments, catalysts, rheologymodifiers, antioxidants, U.V. absorbers, hindered amine lightstabilizers, antioxidants, in particular disubstituted phenoliccompounds, hydroperoxide decomposers, leveling agents, antifoamingagents, anti-cratering agents, adhesion promoting agents are notincluded in the term.

Molecular weight (both number and weight average) is determined by gelpermeation chromatography utilizing a high performance liquidchromatograph supplied by Hewlett-Packard, Palo Alto, Calif. and unlessotherwise stated the liquid phase used was tetrahydrofuran and thestandard was polymethylmethacrylate or polystyrene.

“Tg” (glass transition temperature) is in ° C. and determined byDifferential Scanning Calorimetry or calculated according to the FoxEquation.

Typically the binder of the novel composition comprises 20 to 80% byweight, based on the weight of the binder, of the isocyanate reactivecomponent or aspartic acid derivative and 20 to 80% by weight, based onthe weight of the binder, of a polyisocyanate crosslinking agent. Thestoichiometric ratio of isocyanate functionality to isocyanate reactivecomponent is 0.5 to 3.0, preferably, 0.8 to 2.0 and most preferably, 1.0to 1.5. Optionally, the binder can contain up to 75% by weight,preferably, 5 to 60% by weight, and most preferably, 5 to 30% by weight,based on the weight of the binder, of a polymeric or oligomericcomponent or both wherein the component contains groups that arereactive with the polyisocyanate crosslinking agent. One preferredbinder composition contains 25 to 50%, by weight of the isocyanatereactive component, 5 to 30% by weight of the polymeric or oligomericcomponent or both and 20 to 70% by weight of a polyisocyanate, whereinthe sum of all of the components of the binder is 100%. Anotherpreferred binder composition contains the isocyanate reactive componentas the sole nucleophilic component that is reactive with thepolyisocyanate.

Particular advantages of the novel coating composition of this inventionis that it provides a protective clear finish that has an excellentbalance between pot life and cure characteristics once applied to theobject. Also, the resulting finish has good gloss and distinctness ofimage that provides an excellent appearance. The finish hardens in areasonably short time after application and has excellentweatherability, in particular, resistance to U.V. degradation andphoto-oxidation when properly reinforced with the appropriate additives.When the novel composition is used to refinish automobiles and trucks,it has excellent adhesion to metal substrates and cures to a tack freestate in a relatively short period of time under ambient temperatures orunder slightly elevated drying temperatures, for example, 40 to 100° C.,that allows a coated vehicle to be moved or further processed withoutdamage to the finish.

The novel composition of this invention can contain pigments and isuseful as a pigmented mono-coat topcoat, as a pigmented base coat of abase coat/clear coat finish or as a primer or primer surfacer. Such aprimer or primer surfacer cures in a relatively short period of time toallow for subsequent application of topcoats, basecoat/clear coats ormonocoats. The novel composition can also be used for OEM (originalequipment manufacture) of automobiles, trucks and parts thereof.

The novel composition typically is solvent based and has a solidscontent of film forming binder of 20 to 90% by weight, preferably, 40 to80% by weight. It may be possible to formulate a 100% solids compositionwith the use of reactive diluents or when applied at high viscositiesby, for example, using airless spray equipment or when used as a putty.

An aqueous liquid carrier, which typically is water but may containother liquids, may be used in place of the solvent. Before application,a sufficient amount of liquid usually is added, for example, water orsolvents, to reduce the composition to a spray viscosity. In the eventthe novel coating composition is an aqueous based composition, thecomposition typically has a pH of 6.0 to 10.0 and preferably, 7.5 to8.5.

The present invention provides for a facile synthesis of athermoreversible system useful as coating, where the term“thermoreversible” describes a polymeric network which upon heatingbreaks up which results in disintegration of the polymeric network. Atypical example of such a thermoreversible coating is, for example,described in U.S. Pat. No. 5,633,389 for the formation of a hydantoinfrom an aspartic polyester-urea. Low molecular weight hydantoins arewell known compounds and their uses as intermediates and ingredients inthe chemical, pharmaceutical and consumer product industries. Certaincoatings of this invention comprised of aspartic ester compounds (suchas, structures II to XXVII, shown below), may undergo a thermoreversiblecrosslinking reaction such that the ester-backbone betweenurea-crosslinks is cleaved.

Surprisingly, certain aspartic compounds of this invention do notundergo a thermoreversible crosslinking reaction under conditionscomparable to aspartic ester compounds. It was discovered that compoundswith an amide linkage in the backbone of the molecule and hence betweenthe urea links in the coating film, for example, compounds XXVIII-XLI ofthis invention after crosslinking with isocyanates, do not undergo athermoreversible crosslinking reaction. For example, when crosslinkedcoating films containing aspartic ester compounds, for example, compoundIX, are heated at 140° C. for 30 minutes, the films will lose asignificant amount of crosslinking and become soluble in commonsolvents, such as, methyl ethyl ketone. The urea crosslinking, whichoccurs in these films under the ambient, or slightly elevatedtemperatures shown above, is significantly lost upon heating. Such filmscould be used as a temporary protection barrier, for example, forstorage or transportation or other reasons not mentioned here. On theother hand, aspartic amide compounds (for example, XXVIII-XLI)crosslinked with isocyanates do not lose the urea crosslinking under thesame conditions. This makes it possible to engineer novel coatingcompositions with varying degrees of thermoreversibility by using, forexample, mixtures of aspartic amides and aspartic esters.

The isocyanate reactive component of the novel composition is an aminederivative and has the formula (I)

wherein

-   -   R is a hydrocarbon radical obtained by removing (m+n) hydrogen        atoms from a C₁ to C₂₀ linear or branched alkyl group, or a C₅        to C₁₆ cycloaliphatic group; alternatively, R is a residue        obtained by removing n amino groups from a polyether polyamine        with m equal to 0 having a functionality of n and a number        average molecular weight of less than 600, wherein the amino        groups are attached to primary carbon atoms and the ether groups        are separated by at least two carbon atoms;    -   m equals 0 to 4, and m preferably equals 0, 1 or 2, and n, on        average, equals 1 to 4, and preferably, n, on average, equals 1        and 2, with the proviso that m cannot be 0 unless n equals at        least 2 if r equals 0 and Z does not contain an OH-group, n        equals 1 and r equals 1 and Z does or does not contain an        OH-group, or n equals 1, r equals 0 and Z contains at least one        OH-group;    -   X and Y each can be independently O or NR³;    -   R³ is equal to H, or C₁ to C₂₀ linear or branched alkyl group, a        C₅ to C₁₆ cycloaliphatic group, or R³ is equal to C₃═O if s=0,        i.e., the compound is a cyclic imide;    -   Z is selected from a C₁ to C₂₀ linear or branched alkyl group, a        C₅ to C₁₆ cycloaliphatic group, or an OH-group containing        linear, branched or cycloaliphatic alkyl group, preferred groups        for Z are methyl, propyl, n-butyl, iso-butyl, sec-butyl,        tert-butyl, or cyclohexyl; or Z comprises a fragment of the        structure —CH₂—CHR⁴—R⁵, with R⁴ equal to H, or C₁ to C₂₀ linear        or branched alkyl group, or a C₅ to C₁₆ cycloaliphatic group and        R⁵ equal to —CN or —C(═O)OR⁶, with R⁶ equal to H, or C₁ to C₂₀        linear or branched alkyl group, or a C₅ to C₁₆ cycloaliphatic        group;    -   p and q are equal to 0 or 1, if p and q equal to 1, the —NH—Z        fragment can be bound to either C₁ or C₂, and mixtures of        compounds and isomers are commonly utilized by this invention;    -   s is equal to 0 or 1, with the proviso that s can only be 0 if p        equals 1 and X═NR³ wherein R³ equals C₃═O (cyclic imide);    -   R² is H or independently selected from a C₁ to C₂₀ linear or        branched alkyl group, or a C₅ to C₁₆ cycloaliphatic group;    -   R¹ is a hydrocarbon radical obtained by removing (q+r) hydrogen        atoms from a C₁ to C₂₀ linear or branched alkyl group, or a C₅        to C₁₆ cycloaliphatic group; and    -   r is equal to 0 to 4, and r preferably, equal to 0 or 1.

The following formulas illustrate particularly useful isocyanatereactive components which are amine compounds that are useful in thenovel coating composition of this invention which provide finishes, inparticular, protective clear finishes that have an excellent balancebetween pot life and cure characteristics on application.

Preferred amine compounds used in the novel coating composition of thisinvention are for example the following structures (II) to (XXVII).These structures are defined by formula (I) wherein m=0, X═O, Y═O, R²═H,n=2, p=1, q=1, r=0, s=1, wherein R, R¹ are as defined above, and Z isselected from a C₁ to C₂₀ linear or branched alkyl group, or a C₅ to C₁₆cycloaliphatic group, preferred groups for Z are methyl, propyl,n-butyl, iso-butyl, sec-butyl, tert-butyl, or cyclohexyl.

The amine compounds (II) to (XXVII) are prepared by first reacting adiol, HO—R—OH, with two equivalents maleic anhydride, followed byesterification to form the bis-maleate. Further reaction with a primaryamine component yields the secondary amine compound of this invention.The reaction temperature, conditions and reactant concentration isselected to favor the formation of the double addition product. However,small amounts of half reacted bis-maleate, i.e., an amine-maleateintermediate, may be present in the final product.

In another preferred embodiment, this invention relates to compoundswith, for example, structures (XXVIII) to (XLIII). These structures aredefined by formula (I) with m=0, n=2, X═NH, Y═O, R²═H, p=1, q=1, r=0,s=1, wherein R, R¹ are as defined-above, and Z is selected from a C₁ toC₂₀ linear or branched alkyl group, or a C₅ to C₁₆ cycloaliphatic group,preferred groups for Z are methyl, propyl, n-butyl, iso-butyl,sec-butyl, tert-butyl, or cyclohexyl, preferred groups for R¹ aremethyl, ethyl, propyl, n-butyl, iso-butyl, or cyclohexyl.

The amine compounds (XXVIII) to (XLIII) are prepared by first reacting adiamine, H₂N—R—NH₂, with two equivalents maleic anhydride to form thebis-maleamic acid, followed by esterification of the carboxylic acidgroups. Further reaction with a primary amine component yields thesecondary amine compound of this invention. The reaction temperature,conditions and reactant concentration is selected to favor the formationof the double addition product. However, small amounts of half reactedbis-maleate, i.e. an amine-maleate intermediate, may be present in thefinal product. Compounds (XLI) and (XLIII) are typically formed using acommercial product, Jeffamine®-HK511, which is a mixture of difunctionalprimary amines having an average molecular weight of approximately 220and containing both oxyethylene and oxypropylene groups. The resultingcompounds (XLI) and (XLIII) will each be a mixture of compounds havingthese groups.

Another preferred embodiment of the present invention relates tocompounds with for example structure (XLIV). This structure is definedby formula (I) with m=0, n=2, X═NR³, R²═H, p=1, s=0, wherein R isdefined above, R³ equals C₃═O, and Z is selected from a C₁ to C₂₀ linearor branched alkyl group, or a C₅ to C₁₆ cycloaliphatic group, preferredgroups for Z are methyl, propyl, n-butyl, iso-butyl, sec-butyl,tert-butyl, or cyclohexyl.

Amine compounds similar to (XLIV) are prepared by first reacting adiamine, H₂N—R—NH₂, with two equivalents maleic anhydride to form thebis-maleamic acid, followed by cyclization to the bis-maleimide. Furtherreaction with a primary amine component yields the secondary aminecompound of this invention. The reaction temperature, conditions andreactant concentration is selected to favor the formation of the doubleaddition product.

Another preferred embodiment of this invention relates to compounds withstructure (XLV), having one maleamic ester unit (analogous to XXIX) andone maleimide unit (analogous to (XLIV) within the same molecule,isomers thereof, as well as mixtures of these compounds with either ofthe aforementioned bis-maleamic ester or bis-maleimide compounds.

Compounds, such as, (XLV) are often formed as side-products in thesynthesis of bis-maleate-based compounds (XXVIII-XLIII).

Another preferred embodiment of this invention relates to compoundswith, for example, structures (XLVI) and (XLVII). These structures aredefined by formula (I) with m=0, n=2, X═NR³, Y═O, p=1, q=0, r=0, s=1,wherein R, R¹ and R² are as defined above, R³ equals Me or another alkylgroup, and Z is selected from a C₁ to C₂₀ linear or branched alkylgroup, or a C₅ to C₁₆ cycloaliphatic group. Since the amide-N ismethylated in compounds XLIV and XLV, these compounds will not undergoimide formation such as the aforementioned aspartic amides.

The amine compounds (XLVI) and (XLVII) are prepared by first reacting adiamine, HN(Me)—R—N(Me)H, with two equivalents maleic anhydride to formthe bis-maleamic acid, followed by esterification of the carboxylic acidgroups. Further reaction with a primary amine component yields thesecondary amine compound of this invention. The reaction temperature,conditions and reactant concentration is selected to favor the formationof the double addition product. However, small amounts of half reactedbis-maleate, i.e., an amine-maleate intermediate, may be present in thefinal product.

Another preferred embodiment of this invention relates to compoundswith, for example, structures (XLVIII) to (LI). These structures aredefined by formula (I) with m=0, n=2, X═O, p=0, q=0, r=0, s=1, whereinR, R¹ and R² are as defined above, and Z is selected from a C₁ to C₂₀linear or branched alkyl group, or a C₅ to C₁₆ cycloaliphatic group, orZ comprises a fragment of the structure —CH₂—CHR⁴—R⁵, with R⁴ equal toH, or C₁ to C₂₀ linear or branched alkyl group, or a C₅ to C₁₆cycloaliphatic group and R⁵ equal to —CN or —C(═O)OR⁶, with R⁶ equal toH, or C₁ to C₂₀ linear or branched alkyl group, or a C₅ to C₁₆cycloaliphatic group.

The amine compounds (XLVIII) to (LI) are prepared as isomeric mixturesby first reacting a diol, HO—R—OH, with two equivalents of an aminoacid, followed by functionalization of the amino group via eitherMichael addition to a Michael acceptor (see XLVIII or XLIX), or viareductive amination (see L or LI). The reaction temperature, conditionsand reactant concentration is selected to favor the formation of thedouble addition product, however small amounts of half-reactedintermediate, comprising both functionalized secondary amine andunreacted primary amine groups, may be present.

Another preferred embodiment of this invention relates to compounds withfor example structures (LII) and (LIII). These structures are defined byformula (I) with m=1, n=1, X═O, p=0, q=0, r=0, s=1, wherein R, R¹ and R²are as defined above, and Z is selected from a C₁ to C₂₀ linear orbranched alkyl group, or a C₅ to C₁₆ cycloaliphatic group, or Zcomprises a fragment of the structure —CH₂—CHR⁴—R⁵, with R⁴ equal to H,or C₁ to C₂₀ linear or branched alkyl group, or a C₅ to C₁₆cycloaliphatic group and R⁵ equal to —CN or —C(═O)OR⁶, with R⁶ equal toH, or C₁ to C₂₀ linear or branched alkyl group, or a C₅ to C₁₆cycloaliphatic group.

The amine compounds (LII) and (LIII) are prepared as isomeric mixturesby first reacting a diol, HO—R—OH, with one equivalent of an amino acid,followed by functionalization of the amino group via either Michaeladdition to a Michael acceptor (see LII), or via reductive amination(see LIII).

Another preferred embodiment of this invention relates to compounds withfor example structure (LIV). These structures are defined by formula (I)with m=1, n=1, X═O, Y═O, p=1, q=1, r=0, s=1, wherein R, R¹ and R² are asdefined above, and Z is selected from a C₁ to C₂₀ linear or branchedalkyl group, or a C₅ to C₁₆ cycloaliphatic group.

The amine compounds (LIV) are prepared as isomeric mixtures by reactinga diol, HO—R—OH, with one equivalent of maleic anhydride, followed byesterification of the carboxylic acid group and Michael addition of aprimary amine to the double bond.

Yet another preferred embodiment of this invention relates toaminoalcohol compounds with for example structures (LV-LXV). Thesestructures are defined by formula (I) with m=0, n=1, X═O, Y═NR³, p=1,q=1, r=0, s=1, wherein R, R¹ and R² are as defined above, R² can equalR³, and Z is an OH-group containing linear, branched or cycloaliphaticalkyl group.

Aminoalcohol compounds such as (LV-LXV) are prepared by first reacting aprimary amine with one equivalent of maleic anhydride, followed byesterification of the carboxylic acid group to yield unsaturatedamide-ester. Michael addition of an amino-alcohol to the double bondyields the final product as isomeric mixture.

Another preferred embodiment of this invention relates to compounds withfor example structures (LXVI). These structures are defined by formula(I) with m=1, n=1, X═O, Y═O, p=1, q=1, r=1, s=1, wherein R, R¹ and R²are as defined above and R preferably equals R¹, and Z is selected froma C₁ to C₂₀ linear or branched alkyl group, or a C₅ to C₁₆cycloaliphatic group.

Amine-diols analogous to compound (LXVI) can be prepared by reacting twoequivalents of a diol, HO—R—OH, with one equivalent of maleic acid underacid catalysis, followed addition of a primary amine to the maleatedouble bond.

The novel coating composition can contain optional polymeric components.These components have groups that are reactive with isocyanate and canbe used in an amount of up to 75% by weight, preferably, 1 to 60% byweight, based on the weight of the binder. One preferred polymericcomponent is an acrylic polymer. Typically useful acrylic polymers havea number average molecular weight of about 5,000 to 50,000, a Tg of 10to 80° C. and contain moieties, such as acetoacetate, aldimine,ketimine, mercaptan, hydroxyl, carboxyl, glycidyl and amino groups.Typically useful acrylic polymers are those known in the art and arepolymers of two or more of the following: linear alkyl (meth)acrylateshaving 1 to 12 carbon atoms in the alkyl group, cyclic or branched alkyl(meth)acrylates having 3 to 12 carbon atoms in the alkyl group includingisobornyl (meth)acrylate, hydroxy alkyl (meth)acrylates having 1 to 4carbon atoms in the alkyl group, glycidyl (meth)acrylate, hydroxy aminoalkyl (meth)acrylates having 1 to 4 carbon atoms in the alkyl group, andcan contain styrene, alpha methyl styrene, vinyl toluene,(meth)acrylonitrile (meth)acryl amides, (meth)acrylic acid, (meaningboth acrylic acid and methacrylic acid) trimethoxysilylpropyl(meth)acrylate and the like.

Preferred are hydroxy functional acrylic polymers having a hydroxyequivalent weight of 300 to 1300 and are polymers of hydroxy alkyl(meth)acrylates and one or more of the aforementioned monomers. Onepreferred hydroxy containing acrylic polymer contains 35 to 50% byweight styrene, 15 to 25% by weight ethylhexyl methacrylate and 15 to20% by weight isobornyl methacrylate and 20 to 30% by weighthydroxyethyl methacrylate. A particularly preferred acrylic polymercontains 37% styrene, 20% by weight 2-ethylhexyl methacrylate and 17.5%by weight of isobornyl methacrylate and 25.5% by weight hydroxyethylmethacrylate.

Acrylic oligomers having a number average molecular weight of 300 to3,000 of the aforementioned monomeric components also can be used as theoptional polymeric component. By using monomers and reactants well knownto those skilled in the art, these oligomers can have the one or more ofthe following groups that are reactive with isocyanate: hydroxyl,carboxyl, glycidyl, amine, aldimine, phosphoric acid and ketimine.Typically useful acrylic oligomers are disclosed in FA 1048 Ser. No.10/617,585 filed Jul. 11, 2003, Publication No. U.S. 2004-001009,published on Jan. 15, 2004, which is hereby incorporated by reference.

Polyesters can also be used as the optional polymeric component, suchas, hydroxyl or carboxyl terminated or hydroxyl or carboxyl containingpolyesters. The following are typically useful polyesters or esteroligomers: polyesters or oligomers of caprolactone diol and cyclohexanedimethylol, polyesters or oligomers of tris-hydroxy ethylisocyanurateand caprolactone, polyesters or oligomers of trimethylol propane,phthalic acid or anhydride and ethylene oxide, polyesters or oligomersof pentaerythritol, hexahydrophthalic anhydride and ethylene oxide,polyesters or oligomers of pentaerythritol, hexahydrophthalic anhydrideand butylene oxide, such as those shown in U.S. Pat. No. 6,221,494 B1which is hereby incorporated by reference.

The aforementioned polyesters and oligomers can be reacted with anorganic isocyanate to form urethane polymers and oligomers that can beused as the optional polymeric component in the novel composition.

One useful urethane oligomer that can used in the novel composition isformed by reacting an aliphatic polyisocyanate with an aliphatic orcycloaliphatic monohydric alcohol and subsequently reacting theresulting composition with a hydroxy functional aliphatic carboxylicacid until all of the isocyanate groups have been reacted. One usefulpolyurethane oligomer comprises the reaction product of the isocyanurateof hexane diisocyanate, cyclohexanol and dimethylol propionic acid. Awater dispersible oligomer can be formed using conventional techniquesknow to those skilled in the art.

Optionally, an oligomeric component having a number average molecularweight of 300 to 3,000 having reactive groups that crosslink with anisocyanate, where the reactive groups are hydroxyl, carboxyl, glycidyl,amine, aldimines, phosphoric acid, ketimine and any mixtures thereof canbe added to the novel composition.

Typically useful organic polyisocyanates crosslinking agents that can beused in the novel composition of this invention include aliphaticpolyisocyanates, cycloaliphatic polyisocyanates and isocyanate adducts.

Examples of suitable aliphatic and cycloaliphatic polyisocyanates thatcan be used include the following: 4,4′dicyclohexyl methanediisocyanate, (“H₁₂MDI”), trans-cyclohexane-1,4-diisocyanate,1,6-hexamethylene diisocyanate (“HDI”), isophorone diisocyanate,(“IPDI”), other aliphatic or cycloaliphatic di-, tri- ortetra-isocyanates, such as, 1,2-propylene diisocyanate, tetramethylenediisocyanate, 2,3-butylene diisocyanate, octamethylene diisocyanate,2,2,4-trimethyl hexamethylene diisocyanate, dodecamethylenediisocyanate, omega-dipropyl ether diisocyanate, 1,3-cyclopentanediisocyanate, 1,2 cyclohexane diisocyanate, 1,4 cyclohexanediisocyanate, 4-methyl-1,3-diisocyanatocyclohexane,dicyclohexylmethane-4,4′-diisocyanate, 3,3′-dimethyl-dicyclohexylmethane4,4′-diisocyanate, polyisocyanates having isocyanurate structural units,such as, the isocyanurate of hexamethylene diisocyanate and theisocyanurate of isophorone diisocyanate, the adduct of 2 molecules of adiisocyanate, such as, hexamethylene diisocyanate, uretidiones ofhexamethylene diisocyanate, uretidiones of isophorone diisocyanate and adiol, such as, ethylene glycol, the adduct of 3 molecules ofhexamethylene diisocyanate and 1 molecule of water, allophanates,trimers and biurets of hexamethylene diisocyanate, allophanates, trimersand biurets of isophorone diisocyanate and the isocyanurate of hexanediisocyanate.

Tri-functional isocyanates also can be used, such as, Desmodur® N 3300,trimer of hexamethylene diisocyanate, Desmodur® 3400, trimer ofisophorone diisocyanate, Desmodur® 4470 trimer of isophoronediisocyanate, these trimers are sold by Bayer Corporation. A trimer ofhexamethylene diisocyanate sold as Tolonate® HDT from Rhodia Corporationis also suitable.

An isocyanate functional adduct can be used, such as, an adduct of analiphatic polyisocyanate and a polyol. Also, any of the aforementionedpolyisocyanates can be used with a polyol to form an adduct. Polyols,such as, trimethylol alkanes, particularly, trimethylol propane orethane can be used to form an adduct.

The novel composition can contain 1 to 30% by weight, based on theweight of the binder of acrylic NAD (non-aqueous dispersed) resins.These NAD resins typically are high molecular weight resins having acrosslinked acrylic core with a Tg between 20 to 100° C. and attached tothe core are low Tg stabilizer segments. A description of such NADs isfound in Antonelli et al. U.S. Pat. No. 4,591,533 and in Barsotti et al.U.S. Pat. No. 5,763,528 which patents are hereby incorporated byreference.

Optionally, a catalyst is used in the novel composition to reduce curingtime and temperature and allow curing of the coating at ambienttemperatures. Useful catalysts include alkyl carboxylic acids having 1to 12 carbon atoms in the alkyl group, such as, acetic acid, formicacid, glycolic acid; aromatic acids, such as, benzoic acid; salicylicacid; and oligomers having pendant acid groups.

The coating composition optionally includes a catalytic amount of acatalyst for modifying the curing process. Generally, in the range ofabout 0.001 percent to about 5 percent, preferably in the range of from0.005 percent to 2 percent, more preferably in the range of from 0.01percent to 1 percent of the catalyst is utilized, all in weight percentbased on the total weight of crosslinkable and crosslinking componentsolids. A wide variety of catalysts can be used, such as, tin compounds,including dibutyl tin dilaurate and dibutyl tin diacetate. Thesecatalysts can be used alone or in conjunction with the carboxylic acidsdescribed above, such as, acetic acid. One of the commercially availablecatalysts, sold under the trademark, Fastcat® 4202 dibutyl tin dilaurateby Elf-Atochem North America, Inc. Philadelphia, Pa., is particularlysuitable.

If used as a clear coat or mono-coat, the novel composition optionallycontains about 0.1 to 5% by weight, based on the weight of the binder,of ultraviolet light absorbers. Typically useful ultraviolet lightabsorbers include hydroxyphenyl benzotriazols, such as,2-(2-hydroxy-5-methylphenyl)-2H-benzotriazole,2-(2-hydroxy-3,5-di-tert.amyl-phenyl)-2H-benzotriazole,2[2-hydroxy-3,5-di(1,1-dimethylbenzyl)phenyl]-2H-benzotriazole, reactionproduct of 2-(2-hydroxy-3-tert.butyl-5-methylpropionate)-2H-benzotriazole and polyethylene ether glycol having aweight average molecular weight of 300,2-(2-hydroxy-3-tert.butyl-5-iso-octyl propionate)-2H-benzotriazole;hydroxyphenyl s-triazines, such as,2-[4(2-hydroxy-3-dodecyloxy/tridecyloxypropyl)-oxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine,2-[4(2-hydroxy-3-(2-ethylhexyl)-oxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)1,3,5-triazine,2-(4-octyloxy-2-hydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;hydroxybenzophenone U.V. absorbers, such as, 2,4-dihydroxybenzophenone,2-hydroxy-4-octyloxybenzophenone, and2-hydroxy-4-dodecyloxybenzophenone.

If used as a clear coat or mono-coat, the novel composition optionallycontains about 0.1 to 5% by weight, based on the weight of the binder,of a di-substituted phenol antioxidant or a hydroperoxide decomposer.Typically useful antioxidants includetetrakis[methylene(3,5-di-tert-butylhydroxy hydrocinnamate)]methane,octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate,tris(2,4-di-tert-butylphenyl) phosphite,1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trioneand benzenepropanoic acid, 3,5-bis(1,1-dimethyl-ethyl)-4-hydroxy-C7-C9branched alkyl esters. Typically useful hydroperoxide decomposersinclude Sanko® HCA (9,10-dihydro-9-oxa-10-phosphenanthrene-10-oxide),triphenyl phosphate and other organo-phosphorous compounds, such as,Irgafos® TNPP from Ciba Specialty Chemicals, Irgafos® 168, from CibaSpecialty Chemicals, Ultranox® 626 from GE Specialty Chemicals, MarkPEP-6 from Asahi Denka, Mark HP-10 from Asahi Denka, Irgafos® P-EPQ fromCiba Specialty Chemicals, Ethanox 398 from Albemarle, Weston 618 from GESpecialty Chemicals, Irgafos® 12 from Ciba Specialty Chemicals, Irgafos®38 from Ciba Specialty Chemicals, Ultranox® 641 from GE SpecialtyChemicals and Doverphos® S-9228 from Dover Chemicals.

If used as a clear coat or mono-coat, the novel composition optionallycontains about 0.1-5% by weight, based on the weight of the binder, ofhindered amine light stabilizers. Typically useful hindered amine lightstabilizers include N-(1,2,2,6,6-pentamethyl-4-piperidinyl)-2-dodecylsuccinimide, N(1acetyl-2,2,6,6-tetramethyl-4-piperidinyl)-2-dodecylsuccinimide,N-(2hydroxyethyl)-2,6,6,6-tetramethylpiperidine-4-ol-succinic acidcopolymer, 1,3,5 triazine-2,4,6-triamine,N,N′″-[1,2-ethanediybis[[[4,6-bis[butyl(1,2,2,6,6-pentamethyl-4-piperidinyl)amino]-1,3,5-triazine-2-yl]imino]-3,1-propanediyl]]bis[N,N′″-dibutyl-N′,N′″-bis(1,2,2,6,6-pentamethyl-4-piperidinyl)],poly-[[6-[1,1,3,3-tetramethylbutyl)-amino]-1,3,5-trianzine-2,4-diyl][2,2,6,6-tetramethylpiperidinyl)-imino]-1,6-hexane-diyl[(2,2,6,6-tetramethyl-4-piperidinyl)-imino]),bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidinyl)sebacate,bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl)sebacate,bis(1,2,2,6,6-pentamethyl-4-piperidinyl)[3,5bis(1,1-dimethylethyl-4-hydroxy-phenyl)methyl]butylpropanedioate,8-acetyl-3-dodecyl-7,7,9,9,-tetramethyl-1,3,8-triazaspiro(4,5)decane-2,4-dion,dodecyl/tetradecyl-3-(2,2,4,4-tetramethyl-2l-oxo-7-oxa-3,20-diazaldispiro(5.1.11.2)henicosan-20-yl)propionate.

To form a coating composition that has a high level of weatherabilityand resistance to UV degradation, a combination of above describedultraviolet light absorbers, antioxidants and hindered amine lightstabilizers can be used.

Typically, the composition is a solvent based composition and any of theknown organic solvents may be used to form the coating composition.Typical solvents include aromatic hydrocarbons, such as, toluene,xylene; ketones, such as, acetone, methyl ethyl ketone, methyl isobutylketone, methyl amyl ketone and diisobutyl ketone; esters, such as, ethylacetate, n-butyl acetate, isobutyl acetate; and mixtures of any of theabove.

The novel coating composition may also include other conventionalformulation additives, such as, wetting agents, leveling and flowcontrol agents, for example, Resiflow®S (polybutylacrylate), BYK® 320and 325 (high molecular weight polyacrylates), BYK® 347(polyether-modified siloxane), rheology control agents, such as, fumedsilica, defoamers, surfactants and emulsifiers to help stabilize thecomposition. Other additives that tend to improve mar resistance can beadded, such as, silsesquioxanes and other silicate-basedmicro-particles.

The coating composition of this invention can be used as a clear coatthat is applied over a pigmented base coat that may be a pigmentedversion of the composition of this invention or another type of apigmented base coat. The clear coating can be in solution or indispersion form.

Typically, a clear coating is then applied over the base coating beforethe base coating is fully cured, a so called “wet-on-wet process”, andthe base coating and clear coating are then fully cured at ambienttemperatures or can be cured by heating to elevated temperatures of 40°C. to 100° C. for 15 to 45 minutes or from 40° C. to 170° C. for 15 to45 minutes for those coating of this invention not susceptible tothermoreversible crosslinking. If used in refinishing vehicles, the basecoat may be allowed to “dry to the touch” at ambient temperatureconditions or under warm air before the clear coating is applied. Thebase coating and clear coating preferably have a dry coating thicknessranging from 25 to 75 microns and 25 to 100 microns, respectively. Also,the composition can be used as a matte clear coating composition that istypically applied to the interior of automobiles and trucks.

The novel coating composition may be used as a base coat or as apigmented monocoat topcoat. Both of these compositions require thepresence of pigments. Typically, a pigment-to-binder ratio of 0.1/100 to200/100 is used depending on the color and type of pigment used. Thepigments are formulated into mill bases by conventional procedures, suchas, grinding, sand milling, and high speed mixing. Generally, the millbase comprises pigment and a binder or a dispersant or both in asolventborne or aqueous medium. The mill base is added in an appropriateamount to the coating composition with mixing to form a pigmentedcoating composition.

Any of the conventionally-used organic and inorganic pigments, such as,white pigments, like, titanium dioxide, color pigments, metallic flakes,such as, aluminum flake, special effects pigments, such as, coated micaflakes, coated aluminum flakes and the like and extender pigments can beused. It may be desirable to add flow control additives.

The novel coating composition may be used as a primer or a sealer inwhich case typical pigments used in primers would be added, such as,carbon black, barytes, silica, iron oxide and other pigments that arecommonly used in primers in a pigment-to-binder ratio of 10/100 to300/100. These primers and sealers exhibit exceptional adhesion tountreated bare metal substrates, such as, aluminum and steel substrates,and to treated metal substrates, such as galvanized steel, and provideexcellent stone chip resistance.

The coating composition can be applied by conventional techniques, suchas, spraying, electrostatic spraying, dipping, brushing, and flowcoating.

The coating composition is particularly useful for the repair andrefinish of automobile bodies and truck bodies and parts as a clearcoat, pigmented base coat, mono-coat as a primer, sealer or primersurfacer.

The novel composition has also uses as binder for rapid cure chip coats.The novel composition of this invention can be combined with theisocyanate reagents described above directly without the use of asolvent or additional components and applied to an automobile bodydirectly using application methods known in the art such as integratedmulti-component applicators, spray guns or similar devices. Optionally,the combination of the composition of this invention including thetypical isocyanate component under simple agitation forms a mass with adesired viscosity profile for direct application to a surface, e.g., aputty, using spatulas or other manual application devices, such as asqueegee.

The novel composition has uses for coating any and all itemsmanufactured and painted by automobile sub-suppliers, frame rails,commercial trucks and truck bodies, including but not limited tobeverage bottles, utility bodies, ready mix concrete delivery vehiclebodies, waste hauling vehicle bodies, and fire and emergency vehiclebodies, as well as any potential attachments or components to such truckbodies, buses, farm and construction equipment, truck caps and covers,commercial trailers, consumer trailers, recreational vehicles, includingbut not limited to, motor homes, campers, conversion vans, vans, largecommercial aircraft and small pleasure aircraft, pleasure vehicles, suchas, snow mobiles, all terrain vehicles, personal watercraft,motorcycles, and boats. The novel composition also can be used as acoating for industrial and commercial new construction and maintenancethereof; cement and wood floors; walls of commercial and residentialstructures, such as, office buildings and homes; amusement parkequipment; concrete surfaces, such as parking lots and drive ways;asphalt and concrete road surface, wood substrates, marine surfaces;outdoor structures, such as bridges, towers; coil coating; railroadcars; printed circuit boards; machinery; OEM tools; signs; fiberglassstructures; sporting goods; and sporting equipment.

The following are testing procedures used in the Examples:

Cotton Tack Free Time

Allow coated panel to dry for set period of time (e.g. 30 minutes). Dropa cotton ball from a height of 1 inch onto the surface of the panel andleave the cotton ball on the surface for a set time interval and invertpanel. Repeat above until the time the cotton ball drops off the panelon inversion and note that as the cotton tack free time.

MEK Rubs

A coated panel is rubbed (100 times) with an MEK (methyl ethyl ketone)soaked cloth using a rubbing machine and any excess MEK is wiped off.The panel is rated from 1-10. Rating 10—no visible damage to thecoating, rating 9—1-3 distinct scratches, rating 8—4-6 distinctscratches, rating 7—7-10 distinct scratches, rating 6—10-15 distinctscratches with slight pitting or slight loss of color, rating 5—15-20distinct scratches with slight to moderate pitting or moderate loss ofcolor, rating 4—scratches start to blend into one another, rating 3—onlya few undamaged areas between blended scratches, rating 2—no visiblesigns of undamaged paint, rating 1 complete failure—bare spots areshown. The final rating is obtained by multiplying the number of rubs bythe rating.

Water Spot Test

Water spot rating is a measure of how well the film is crosslinked earlyin the curing of the film. If water spot damage is formed on the film,this is an indication that the cure is not complete and further curingof the film is needed before the film can be wet sanded or buffed ormoved from the spray both. The water spot rating is determined in thefollowing manner.

Coated panels are laid on a flat surface and deionized water was appliedwith a pipette at 1 hour-timed intervals. A drop about ½ inch indiameter was placed on the panel and allowed to evaporate. The spot onthe panel was checked for deformation and discoloration. The panel waswiped lightly with cheesecloth wetted with deionized water, which wasfollowed by lightly wiping the panel dry with the cloth. The panel wasthen rated on a scale of 1 to 10. Rating of 10 best—no evidence ofspotting or distortion of discoloration, rating 9—barely detectable,rating 8—slight ring, rating 7—very slight discoloration or slightdistortion, rating 6—slight loss of gloss or slight discoloration,rating 5—definite loss of gloss or discoloration, rating of 4—slightetching or definite distortion, rating of 3—light lifting, bad etchingor discoloration, rating of 2—definite lifting and rating of1—dissolving of the film.

BK Dry Time

Surface drying times of coated panels measured according to ASTM D5895.

Swell Ratio

The swell ratio of a free film (removed from a sheet ofTPO—thermoplastic olefin) was determined by swelling the film inmethylene chloride. The free film was placed between two layers ofaluminum foil and using a LADD punch, a disc of about 3.5 mm in diameterwas punched out of the film and the foil was removed from the film. Thediameter of the unswollen film (D_(o)) was measured using a microscopewith a 10× magnification and a filar lens. Four drops of methylenechloride were added to the film and the film was allowed to swell for afew second and then a glass slide was placed over the film and theswollen film diameter (D_(s)) was measured. The swell ratio was thencalculated as follow:Swell Ratio=(D _(s))²/(D _(o))²Persoz Hardness Test

The change in film hardness of the coating was measured with respect totime by using a Persoz hardness tester Model No. 5854 (ASTM D4366),supplied by Byk-Mallinckrodt, Wallingford, Conn. The number ofoscillations (referred to as Persoz number) were recorded.

Hardness (Fischer)

Hardness was measured using a Fischerscope® hardness tester (themeasurement is in Newtons per square millimeter).

Gel Fraction

Measured according to the procedure set forth in U.S. Pat. No. 6,221,494col. 8 line 56 to col. 9 line 2 which procedure is hereby incorporatedby reference.

Direct to Metal Adhesion Test

Adhesion of a coating to bare metal substrates was determined accordingto ASTM D3359-02, the standard test method for measuring adhesion bytape test.

Time to Gel

The time in minutes it takes for a liquid coating to gel.

Infra Red Film Cure

The infra Red spectrum was taken of the films made from certain coatingexamples. The spectra were taken on films cured for 10 days at ambientroom temperature conditions, after curing for 30 minutes at 140° C., andin some instances, after curing at ambient temperature conditions for 10days followed by heating for 30 minutes at 140° C.

The present invention is further defined in the following Examples. Itshould be understood that these Examples are given by way ofillustration only. From the above discussion and these Examples, oneskilled in the art can ascertain the essential characteristics of thisinvention, and without departing from the spirit and scope thereof, canmake various changes and modifications of the invention to adapt it tovarious uses and conditions. As a result, the present invention is notlimited by the illustrative examples set forth herein below, but ratheris defined by the claims contained herein below.

In the following examples, all parts and percentages are on a weightbasis unless otherwise indicated.

EXAMPLES

The following were used in the examples:

LC/MS (Liquid Chromatography/Mass Spectroscopy) analyses were performedon a Waters Alliance 2790 LC quipped with a MS (ES) interface. Column:Zorbax SB-C18, 2.1×150 mm at 50° C.; Solvents: A=99:1water/acetonitrile, B=acetonitrile, C=methanol, D=80:20acetonitrile/water; Conditions: 90% A/10% B/0.25% D to 0% A/100% B/0.25%D over 30 min, hold ten minutes, then return to initial conditions after42 min; Wavelength: 191-799 nm; Flow rate: 0.25 mL/min.

¹H NMR and ¹³C NMR spectra were recorded on a Bruker Avance 400spectrometer. ¹H NMR and ¹³C NMR chemical shifts were referenced toresidual ¹H and ¹³C signals of the deuterated solvents.

General Preparation Procedure for Compounds (II)-(VII):

To a four-neck 2 L RBF (round bottom flask) fitted with an overheadstirrer, condenser and thermocouple was added under N2 maleic anhydride(86.5 g, 0.84 mol), 500 mL toluene, and 1,6-hexanediol (50.0 g, 0.42mol). The reaction mixture was then heated to 60° C. Within one hour, awhite precipitate began to form, and the reaction was allowed to proceedovernight. The reaction mixture was then filtered through a coarse frit,and the resulting white solid was rinsed with little toluene and driedto constant weight. 129.8 g (99% yield) of the desired product,(Z)-2-Butenedioic-acid-1,6-hexanediyl-ester, was obtained (13C NMR 125MHz, DMSO—dimethyl sulfoxide): δ 166.4, 165.2, 131.2, 128.8, 64.4, 27.7,25.0)

In the second step, this compound was transformed into the dimethylesterfollowing standard procedures such as reaction with Mel (Me₂SO₄)/K₂CO₃.To a four-neck 3 L RBF fitted with an overhead stirrer, addition funneland thermocouple was added under N₂(Z)-2-Butenedioic-acid-1,6-hexanediyl-ester (93.0 g, 0.30 mol) and 800mL of DMF (dimethyl formamide). The mixture was stirred until the solidhad dissolved before 98.2 g of K₂CO₃ (0.71 mmol, 2.4 eq.) was added. Thereaction mixture was cooled in an ice bath to 0° C., and methyl iodide44.2 mL (0.71 mol, 2.4 eq.) was added dropwise. The reaction mixture wasstirred at room temperature overnight before it was filtered through abed of celite. The DMF solvent was reduced by rotary evaporation, theresidue was taken up in 1.5 L of ethyl acetate, washed with 4×1 L 5%KHSO₄, 2×1 L of half-saturated NaHCO₃, 2×1 L of brine, dried over MgSO₄,filtered and concentrated. The residual brown oil was purified bychromatography on 600 g silica gel packed with 25% ethyl acetate inhexane. The dimethyl ester (R_(f)=0.28) was obtained in 31% yield as apale yellow oil. (¹³C NMR (125 MHz, CDCl₃=chloroform-d): δ 165.7, 165.2,130.0, 129.5, 65.2, 52.1, 28.3, 25.5).

Diamines (II-VII) were then synthesized from the dimethyl ester byreaction in acetonitrile with excess amine at 50° C. For example,diamine (II) was synthesized in quantitative yield according to LC/MS(Liquid Chromatograph/Mass Spectoscopy) from 1.3 g (3.8 mmol) dimethylester and 1.54 mL (4 eq.) cyclohexylamine in 2 mL of acetonitrile after16 h at 50° C., followed by solvent removal and removal of excess aminein vacuo.

Diamine (III) was synthesized in an analogous fashion from the dimethylester and secButyl amine, diamine (IV) from the dimethyl ester andnButyl amine, diamine (V) from the dimethyl ester and isoButyl amine,diamine (VI) from the dimethyl ester and neopentyl amine, diamine (VII)from the dimethyl ester and tertButyl amine.

General Preparation Procedure for Compounds (VIII)-(XIV):

To a four-neck 2 L round bottom flask fitted with an overhead stirrer,condenser and thermocouple was added under N₂ 1,4-cyclohexane dimethanol(110.0 g, 0.76 mol), 600 mL acetonitrile, and maleic anhydride (196.8 g,1.91 mol). The reaction mixture was then heated to 50° C., and thereaction was allowed to proceed for three days. A large amount of awhite precipitate had formed. The reaction mixture was filtered hotthrough a coarse frit, and the residue was washed with someacetonitrile. The white solid was dried under N₂ to constant weight, and161.5 g (62% yield) of the desired product,(Z)-2-Butenedioic-acid-1,4-cyclohexanediylbis(methylene) ester, wasobtained as characterized by LC/MS analysis. The overall yield wasimproved 80% by subsequent crystallizations from the mother liquor.

In the second step, this compound was transformed into the dimethylesterfollowing standard procedures such as reaction with Mel (Me₂SO₄)/K₂CO₃.To a four-neck 1 L RBF fitted with stir bar, addition funnel andthermocouple was added under N₂(Z)-2-Butenedioic-acid-1,4-cyclohexanediylbis(methylene) ester (27.4 g,0.08 mol) and 200 mL of DMF. The mixture was stirred until the solid haddissolved before 26.7 g of K₂CO₃ (0.19 mmol, 2.4 eq.) was added. Thereaction mixture was cooled in an ice bath to 0° C., and methyl iodide(12 mL, 0.19 mol, 2.4 eq.) was added dropwise. The reaction mixture wasstirred at room temperature overnight before it was filtered through abed of celite. The DMF solvent was reduced by rotary evaporation, theresidue was taken up in 1 L of ethyl acetate and washed with 2×150 mL 5%KHSO₄. After back-extraction using 2×500 mL ethyl acetate, the organiclayers were combined, washed with 3×500 mL DI water, 2×150 mL of 5%NaHCO₃, 2×150 mL of brine, dried over MgSO₄, filtered and concentrated.The residual yellow solid was purified by recrystallization from ethylacetate/hexane, yielding 14.0 g of the dimethyl ester as white solid(47% yield) in >98% purity according to LC/MS. (¹³C NMR (125 MHz,CDCl₃): δ 165.7, 165.2, 129.8, 129.7, 70.2, 52.1, 36.9, 28.8).

Diamines (VIII-XIV) were then synthesized from the dimethyl ester byreaction in acetonitrile with excess amine at 50° C. For example,diamine (IX) was synthesized in quantitative yield according to LC/MSfrom 1.3 g (3.8 mmol) dimethyl ester and 1.54 mL (4 eq.) secbutylaminein 2 mL of acetonitrile after 16 h at 50° C., followed by solventremoval and removal of excess amine in vacuo. Diamine (VIII) wassynthesized in an analogous fashion from the dimethyl ester andcyclohexyl amine, diamine (X) from the dimethyl ester and nButyl amine,diamine (XI) from the dimethyl ester and isobutyl amine, diamine (XII)from the dimethyl ester and neopentyl amine, diamine (XIII) from thedimethyl ester and tertbutyl amine, and diamine (XIV) from the dimethylester and (2-methylbicyclo[2.2.1]heptan-2-yl)methanamine.

General Preparation Procedure for Compounds (XV)-(XIX and (XXVII):

To a four-neck 2 L round bottom flask fitted with an overhead stirrer,condenser thermocouple, and two addition funnels was added under N₂1,4-cyclohexanedimethanol (35.4 g, 0.24 mol) and 1000 mL dry THF(tetrahydrofuran). Then PPh₃ (triphenylphosphine) (127.3 g, 0.49 mol)was added. The reaction mixture was cooled to −10° C., followed by slowaddition of diisopropylazodicarboxylate (DIAD, 95%, 103.3 g, 0.49 mol).The solution became very viscous and eventually precipitated a yellowsolid, then it was allowed to warm up to room temperature where it wasstirred for about 10 minutes. The reaction mixture was cooled again to−10° C., followed by dropwise addition of monobutyl maleate (83.5 g,0.49 mol), causing the yellow solid to dissolve again. The resultingorange solution was allowed to warm up to room temperature and stirredovernight. After work-up, the crude reaction product was chromatographedon silica (25% ethyl acetate/hexanes) (R_(f)=0.47), yielding 58.4 g ofthe desired bis-maleate as a pale yellow oil, which will eventuallysolidify (53% yield). (¹³C NMR (125 MHz, CDCl₃): δ 165.33, 165.30,129.9, 129.6, 70.1, 68.0, 65.2, 36.9, 34.4, 30.5, 28.8, 25.3, 19.1,13.7).

Diamines (XV-XIX and XXVII) were then synthesized from the dibutyl esterby reaction in acetonitrile with excess amine at 50° C. For example,diamine (XVI) was synthesized in quantitative yield according to LC/MSfrom 1.23 g (2.7 mmol) dibutyl ester and 0.93 mL (3 eq.) sec-Butylaminein 1.5 mL of acetonitrile after 17 h at 50° C., followed by solventremoval and removal of excess amine in vacuo. Diamine (XV) wassynthesized in an analogous fashion from the dibutyl ester andcyclohexyl amine, diamine (XVII) from the dibutyl ester and nButylamine, diamine (XVIII) from the dibutyl ester and isoButyl amine,diamine (XIX) from the dibutyl ester and neopentyl amine, and diamine(XXVII) from the dibutyl ester and(2-methylbicyclo[2.2.1]heptan-2-yl)methanamine.

General Preparation Procedure for Compounds (XX)-(XXVI):

To a four-neck 2 L round bottom flask fitted with an overhead stirrer,condenser thermocouple, and two addition funnels was added under N21,4-cyclohexanedimethanol (34.8 g, 0.24 mol) and 650 mL dry THF. ThenPPh3 (126.6 g, 0.48 mol) was added. The reaction mixture was cooled to−10° C., followed by slow addition of diisopropylazodicarboxylate (DIAD,95%, 102.7 g, 0.48 mol). The solution was allowed to warm up to roomtemperature where it was stirred for about 10 minutes. The reactionmixture was cooled again to −10° C., followed by dropwise addition ofmonocyclohexyl maleate (95.6 g, 0.48 mol) in 400 mL of dry THF, causinga yellow precipitate that had formed during the DIAD addition todissolve again. The resulting orange solution was allowed to warm up toroom temperature and stirred for three days. The solvent was removed byrotary evaporation leaving 390.1 g of brown oil behind that wastriturated with 600 mL of diethyl ether. After filtration, diethyl etherwas removed by rotary evaporation to yield 164 g of a pink solid thatwas subsequently chromatographed on silica (25% ethyl acetate/hexanes)(Rf=0.54), yielding 54.0 g of the desired bis-maleate as a white (44%yield). (¹³C NMR (125 MHz, CDCl₃): δ 165.3, 164.7, 130.5, 129.2, 73.9,70.1, 67.9, 36.9, 34.4, 31.5, 28.8, 25.3, 23.8).

Diamines (XX-XXVI) were then synthesized from the dicyclohexyl ester byreaction in acetonitrile with excess amine at 50° C. For example,diamine (XXI) was synthesized in quantitative yield according to LC/MSfrom 31.5 g (0.06 mol) dicyclohexyl ester and 27.4 g (0.38 mol, 6 eq.)sec-Butylamine in 210 mL of dry acetonitrile after four days at 50° C.,followed by solvent removal and removal of excess amine in vacuo. Afterfiltration of the light hazy pale yellow oil, 38.0 g of diamine productwere obtained in >96% purity according to LC/MS analysis (94% yield).Diamine (XX) was synthesized in an analogous fashion from thedicyclohexyl ester and cyclohexyl amine, diamine (XXII) from thedicyclohexyl ester and nButyl amine, diamine (XXIII) from thedicyclohexyl ester and isoButyl amine, diamine (XXIV) from thedicyclohexyl ester and nopentyl amine, diamine (XXV) from thedicyclohexyl ester and tertButyl amine, and diamine (XXVI) from thedicyclohexyl ester and (2-methylbicyclo[2.2.1]heptan-2-yl)methanamine.

General Preparation Procedure for Compounds (XXVIII)-(XLIII):

To a four-neck 250 mL RBF fitted with stirbar, condenser andthermocouple was added under N₂ DYTEK® amine(2-methylpentane-1,5-diamine) (10 g, 0.08 mol) and 10 mL dryacetonitrile, followed by maleic anhydride (17.5 g, 0.17 mol), resultingin an exothermic reaction and formation of a large amount of whitesolid. The reaction mixture was stirred for three hours, before thewhite solid was filtered off, washed with acetonitrile and dried toconstant weight. 22.4 g product (84% yield) was obtained as a mixture ofthe bis-maleamic acid and the mono-maleamic-acid-mono-maleimideaccording to LC/MS analysis. (¹³C NMR (125 MHz, CDCl₃): δ 165.5, 165.4,165.3, 132.9, 132.8, 131.80, 131.78, 45.0, 32.2, 31.0, 25.7, 17.5).

To a three-neck 100 mL RBF fitted with stirbar, addition funnel andthermocouple was added under N₂ DYTEK® bis-maleamic acid (5 g, 0.012mol) and 20 mL of methanol. To this white slurry was added dropwise 38mL of 1.25 M HCl in methanol. Most of the solid dissolved during theaddition and eventually all was dissolved. After two hours, the solventwas removed by rotary evaporation, yielding 6.2 g of yellow oil. Thecrude oil was taken up in 50 mL of CH₂Cl₂, extracted with sodiumbicarbonate solution, back-extracted into CH₂Cl₂, dried over magnesiumsulfate and filtered. The solvent was removed by rotary evaporation,yielding 4.9 g of a pale yellow oil in >94% purity according to LC/MS asmixture of the bis-ester and mono-ester-mono-imide.

Diamines (XXVIII)-(XXXIII) were then synthesized from the bis-maleamicester by reaction in acetonitrile with excess amine at 50° C. Forexample, diamine (XXIX) was synthesized from 62.9 g (0.19 mol)bis-maleamic ester and 57 mL (3 eq.) sec-Butylamine in 300 mL of dryacetonitrile after 2 days at 50° C., followed by solvent removal andremoval of excess amine in vacuo. The resulting brown oil was thenpurified by chromatography on silica (50% ethyl acetate/hexanes),yielding 47.5 g of a diamine product mixture as a yellow oil (53%yield). Diamine (XXVIII) was synthesized in an analogous fashion fromthe bis-maleamic ester and Cyclohexyl amine, diamine (XXX) from thebis-maleamic ester and nButyl amine, diamine (XXXI) from thebis-maleamic ester and isoButyl amine, diamine (XXXII) from thebis-maleamic ester and Neopentyl amine, and diamine (XXXIII) from thebis-maleamic ester and tertButyl amine,

Diamines (XXXIV)-(XXXV) were synthesized in an analogous reactionstarted from the DYTEK® bis-maleamic acid: to a three-neck 100 mL RBFfitted with stirbar, addition funnel and thermocouple was added under N₂DYTEK® bis-maleamic acid and 20 mL of ethanol (XXXIV) or isopropanol(XXXV). To this white slurry was added dropwise 38 mL of 1:25 M HCl inethanol (XXXIV) or isopropanol (XXXV). Most of the solid dissolvedduring the addition and eventually all was dissolved. After two hours,the solvent was removed by rotary evaporation, yielding a yellow oil.The crude oil was taken up in 50 mL of CH₂Cl₂, extracted with sodiumbicarbonate solution, back-extracted into CH₂Cl₂, dried over magnesiumsulfate and filtered. The solvent was removed by rotary evaporation,yielding in both cases a pale yellow oil in as mixture of the bis-esterand mono-ester-mono-imide.

Diamines (XXXIV)-(XXXV) were then synthesized from the bis-maleamicester (ethyl-ester for XXXIV, iso-propyl-ester for XXXV) by reaction inacetonitrile with excess sec-butyl amine at 50° C. as described above.

Diamines (XXXVI-XXXIX) were synthesized following an analogous procedurestarting from 2,2-dimethyl-1,3-propanediamine, which was first convertedinto the bis-maleamic acid by reaction with maleic anhydride inacetonitrile. Subsequent methylation of the carboxylic ester functionalgroups with HCl/MeOH led to the formation of the bis-maleate, which wasthen treated with primary amine. Diamine (XXXVI) was synthesized fromthe bis-maleamic ester and secButyl amine, diamine (XXXVII) from thebis-maleamic ester and neopentyl amine, diamine (XXXVIII) from thebis-maleamic ester and cyclohexyl amine, and diamine (XXXIX) from thebis-maleamic ester and tertButyl amine.

Finally, diamines (XL-XLIII) were synthesized following an analogousprocedure starting from (4-(aminomethyl)cyclohexyl)methanamine (XL) andJeffamine HK511 (XLI-XLIII), the latter being a mixture of isomers.

General Preparation Procedure for Compound (XXXVI)

To a four-neck 3000 mL RBF fitted with overhead stirrer, additionfunnel, reflux condenser, and thermocouple, under N2, was added maleicanhydride (131.3 g, 1.27 mol, 2 eq.) and dry acetonitrile (700 mL),followed by the dropwise addition of 2,2-dimethyl-1,3-propanediamine(76.4 mL, 0.636 mol, 1 eq.), maintaining <50° C. The addition caused asticky white precipitate to form. The reaction was heated to 50° C. for2 hours, then stirred overnight at room temperature. LC/MS (ES+) of analiquot after 17 hours showed the desired product, a small amount ofmono-addition product, and some ring-closed maleimide material. Theprecipitate was filtered, rinsed with fresh acetonitrile, and dried toconstant weight, giving 113.5 g (60%) of the product as a white solid.An additional 11.5 g of product was recovered from the mother liquor fora total of 125.0 g (66%). LC/MS (ES+) shows M+H for the desired product,with some ring-closed material.

To a four-neck 2000 mL RBF fitted with overhead stirrer, additionfunnel, reflux condenser, and thermocouple, under N₂, was added theproduct from step 1 (50.0 g, 0.168 mol, 1 eq.) and dry methanol (500mL), followed by the slow addition of 2M hydrogen chloride in diethylether (210 mL, 0.419 mol, 2.5 eq.), maintaining <20° C. After 1 hour,the starting material had dissolved. The reaction was stirred overnightat room temperature. An aliquot removed for LC/MS (ES+), showed nostarting material. The reaction was concentrated at 35° C. The residuewas taken up in methylene chloride (750 mL), then made slightly basic bydropwise addition of saturated sodium bicarbonate (1 L), maintaining<25° C. by the addition of a small amount of wet ice. The layers wereseparated, and the aqueous was extracted with methylene chloride (1×500mL). The combined organic phases were dried over magnesium sulfate,filtered, and concentrated in vacuo at 35° C., giving the di-ester as aslightly cloudy yellow oil (47.2 g) in 86% yield.

To a four-neck 500 mL RBF fitted with stir bar, condenser, additionfunnel, and thermocouple, under N₂, was added the di-ester from step 2(33.8 g, 0.104 mol, 1 eq.) and dry acetonitrile (150 mL), followed bythe dropwise addition of sec-butylamine (22 mL, 0.218 mol, 2.1 eq.). Thereaction was heated to 50° C. and was stirred overnight at thattemperature. The reaction was monitored by LC/MS (ES+), addingadditional sec-butylamine (10.4 mL, 0.104 mol, 1.0 eq.) to drive thereaction to completion. The reaction was cooled to room temperature,then concentrated in vacuo at 45° C., giving the crude product as alight brown oil. Flash chromatography on silica gel, using a gradient of25% ethyl acetate in hexanes to 100% ethyl acetate, giving the productas a yellow oil in 70% yield. The oil was filtered over Celite to removeresidual silica gel.

General Preparation Procedure for Compound (XLI)

Compound XLI (component of the mixture shown)

To a four-neck 3000 mL RBF fitted with overhead stirrer, additionfunnel, reflux condenser, and thermocouple, under N₂, was added maleicanhydride (304.7 g, 3.11 mol, 2 eq.) and dry acetonitrile (1.5 L). Thereaction was cooled to −5° C. and Jeffamine HK-511 from Huntsman (342.3g, 1.55 mol, 1 eq.) was added dropwise, maintaining <2° C. When theaddition was complete, the reaction was warmed to room temperature andwas stirred overnight. GC and LC/MS (ES+) of an aliquot after 17 hoursshowed no starting material and little mono-addition product. Thereaction was concentrated in vacuo at 35° C., giving 677.4 g (>100%) ofthe product as a viscous orange oil. LC/MS (ES+) shows M+H for thedesired products.

To a four-neck 2000 mL RBF fitted with overhead stirrer, additionfunnel, reflux condenser, and thermocouple, under N₂, was added theproduct from step 1 (168.0 g, 0.403 mol, 1 eq.) and dry methanol (500mL), followed by the slow addition of 2M hydrogen chloride in diethylether (605 mL, 1.21 mol, 3 eq.), maintaining <25° C. An aliquot, removedat 2 hours for LC/MS (ES+), showed no starting material or mono-additionproduct. The reaction was diluted with methylene chloride (1 L), and wastransferred to a four-neck 5000 mL stirring separatory funnel. It wasmade slightly basic by the dropwise addition of saturated sodiumbicarbonate (1.8 L), maintaining <25° C. by the addition of a smallamount of wet ice. The layers were separated, and the aqueous wasextracted with methylene chloride (4×1 L). The combined organic phaseswere dried over magnesium sulfate, filtered, and concentrated in vacuoat 28° C., giving a yellow oil (158.2 g) in 88% yield.

To a four-neck 2000 mL RBF fitted with overhead stirrer, condenser,addition funnel, and thermocouple, under N₂, was added the product fromstep 2 (335.0 g, 0.754 mol, 1 eq.) and dry acetonitrile (600 mL),followed by the dropwise addition of sec-butylamine (168 mL, 1.66 mol,2.2 eq.). The addition caused an exotherm to ˜37° C. When thetemperature had stabilized, the reaction was heated to 50° C. and wasstirred overnight at that temperature. The reaction was monitored byLC/MS (ES+), adding additional sec-butylamine (60 mL, 0.59 mol, 0.8 eq.)to drive the reaction to completion. The reaction was then cooled toroom temperature and concentrated in vacuo at 30° C., giving the productmixture as a light brown oil (427.0 g) in 96% yield.

General Preparation Procedure for Compound (XLVI)

To a four-neck 2000 mL RBF fitted with overhead stirrer, additionfunnel, reflux condenser, and thermocouple, under N₂, was added maleicanhydride (75 g, 0.734 mol, 2.5 eq.) and dry acetonitrile (400 mL),followed by the dropwise addition of N,N′-dimethyl-1,6-hexanediamine(51.9 mL, 0.294 mol, 1 eq.), maintaining <30° C. The reaction turned anorange color as the addition progressed. The reaction was heated to 45°C. for 2 hours, then stirred overnight at room temperature. By morning,a tan solid had precipitated. It was filtered, then dried to constantweight, giving 87.6 g (87%) of the desired product as an off-whitesolid.

To a four-neck 3000 mL RBF fitted with overhead stirrer, additionfunnel, reflux condenser, and thermocouple, under N₂, was added theproduct from step 1 (85.8 g, 0.252 mol, 1 eq.) and dry methanol (875mL), followed by the slow addition of 2M hydrogen chloride in diethylether (630 mL, 1.26 mol, 5 eq.), maintaining <20° C. The reaction wasstirred overnight at room temperature. An aliquot removed for LC/MS(ES+), showed no starting material or mono-addition product. Thereaction was concentrated at 35° C. The residue was taken up inmethylene chloride (1000 mL), then made slightly basic by the dropwiseaddition of saturated sodium bicarbonate (1.5 L), maintaining <25° C. bythe addition of a small amount of wet ice. The layers were separated,and the aqueous was extracted with methylene chloride (1×500 mL). Thecombined organic phases were dried over magnesium sulfate, filtered, andconcentrated in vacuo at 35° C., giving the di-ester as a yellow oil(78.9 g) in 85% yield.

To a four-neck 500 mL RBF fitted with stir bar, condenser, additionfunnel, and thermocouple, under N₂, was added the product from step 2(35.0 g, 0.095 mol, 1 eq.) and dry acetonitrile (150 mL), followed bythe dropwise addition of sec-butylamine (24 mL, 0.238 mol, 2.5 eq.). Theaddition caused no an exotherm to occur, but the reaction becameslightly cloudy. The reaction was heated to 50° C. and was stirredovernight at that temperature. The reaction was monitored by LC/MS(ES+), adding additional sec-butylamine (14.4 mL, 0.143 mol, 1.5 eq.) todrive the reaction to completion. The reaction was cooled to roomtemperature concentrated in vacuo at 33° C., giving the crude product asa light brown oil. Flash chromatography on silica gel, using a gradientof 50% ethyl acetate in hexanes to 100% ethyl acetate to 20% acetone inethyl acetate gave 37.0 g of the product as a yellow oil (66%). The oilwas filtered over Celite to remove residual silica gel, and the finalproduct was characterized by LC/MS (ES+).

General Preparation Procedure for Compound (XLIX):

L,L-Leucine 1,4-cyclohexane dimethanol diester

L-leucine (22.73 g, 264 mmol), 1,4-cyclohexanedimethanol (17.58 g, 120mmol) and p-toluenesulfonic acid monohydrate (57.08 g, 300 mmol) wereadded to a three-neck RBF and 100 ml toluene was added to the mixture. ADean-Stark trap with a reflux condenser was then attached to the flaskwith the receiving side filled to overflow point with toluene undernitrogen. The temperature was increased to 150° C. and the mixture wasrefluxed for 24 h. The reaction mixture was cooled to room temperatureand more L-leucine (8.26 g, 96 mmol) and p-toluenesulfonic acidmonohydrate (19.04 g, 100 mmol) was added to it, followed by refluxingfor another 6 h to drive the reaction to completion. After cooling thereaction to room temperature, the toluene solvent was removed undervacuum and careful neutralization of the residue was carried out usingaqueous sodium bicarbonate solution at 60° C. The mixture was thenextracted with dichloromethane (3×200 ml), the combined organic layerswere dried over sodium sulfate, and the solvent was removed to give aquantitative yield of the product, which was used without furtherpurification.

To L,L-Leucine 1,4-cyclohexanedimethanol diester (3.7 g, 10 mmol) andtriethyl amine (2.8 ml, 20 mmol) at room temperature was added methylacrylate (1.29 g, 15 mmol) and the resulting mixture was stirred at 80°C. for 1 day, after which more triethyl amine (2.8 ml, 20 mmol) andmethyl acrylate (1.29 g, 15 mmol) was added, and the reaction wasstirred for two more 2 days. Removal of volatile material under vacuumfollowed by chromatography on silica using 1:1 ethyl acetate-hexanemixture with 5-10% acetone gave 4.3 g (79%) of the desired adduct(XLIX).

General Preparation Procedure for Compound (LI)

To L,L-Leucine 1,4-cyclohexanedimethanol diester (3.7 g, 10 mmol) in 15ml methanol was added while stirring at room temperature first acetone(3.48 g, 60 mmol) and then 100 ml 1M sodium cyanoborohydride in THF, andthe resulting mixture was allowed to stir at 60° C. for 3 days. Aftercooling to room temperature the reaction mixture was concentrated undervacuum, taken up in dichloromethane (100 ml) and washed with water (100ml). The organic layer was dried over MgSO₄, concentrated under vacuumand purified by chromatography over silica using 1:1 ethylacetate-hexane mixture with 2-5% acetone yielding 3.2 g (71%) of thedesired product (LI).

General Preparation Procedure for Compound (LIII):

L-(4-(hydroxymethyl)cyclohexyl)methyl 2-amino-4-methylpentanoate

L-leucine (8.61 g, 100 mmol), 1,4-cyclohexanedimethanol (18.1 g, 120mmol) and p-toluenesulfonic acid monohydrate (28.56 g, 150 mmol) weretaken in a three neck round bottom flask and 100 ml toluene was added tothe mixture. Dean-stark trap with a reflux condenser was then attachedto the flask with the receiving side filled to overflow point withtoluene under nitrogen. Temperature was increased to 150° C. and themixture refluxed for 24 h. After cooling the reaction to roomtemperature toluene was removed under vacuum and careful neutralizationof the residue was carried out using aqueous sodium bicarbonatesolution. The mixture was then extracted with dichloromethane (3×200ml), the combined organic layers were dried over sodium sulfate, and thesolvent was removed to give a mixture of mono and diester products andpredominantly mono-ester. The reaction mixture was used without furtherpurification.

(4-(hydroxymethyl)cyclohexyl)methyl2-(2-(methoxycarbonyl)ethylamino)-4-methyl pentanoate

To the crude mixture containing predominantlyL-(4-(hydroxymethyl)cyclohexyl)methyl 2-amino-4-methylpentanoate (2.57g, 10 mmol) was added triethyl amine (2.8 ml, 20 mmol) and methylacrylate (1.29 g, 15 mmol) at room temperature and the resulting mixturewas stirred at 80° C. for 2 days. Removal of volatile material undervacuum followed by chromatography over silica using 1:1 ethylacetate-hexane mixture with 2-5% acetone gave 1.58 g (46%) of thedesired product.

General Preparation Procedure for Compound (LVII):

3-(sec-butylcarbamoyl)acrylic acid

To a stirred solution of maleic anhydride, 95% (42.1 g, 0.4 mol) in 500mL diethyl ether at 0° C. was added drop wise sec-butyl amine (29.25 g,0.4 mol) in 50 mL diethyl ether. The resulting mixture was stirred whilea solid formed, which was recovered by filtration. The residue waswashed with 2×100 mL diethyl ether and dried to yield 51.76 g of thedesired compound.

Methyl 3-(sec-butylcarbamoyl)acrylate

To 3-(sec butylcarbamoyl)acrylic acid (20 g, 117 mmol) at roomtemperature was added 150 mL 1.2M HCl in methanol. The resulting mixturewas stirred for two hours. Solvents were removed in vacuo to give thedesired ester, which was used without further purification.

Methyl 3-(sec-butylcarbamoyl)-2-(6-hydroxyhexylamino)propanoate

To methyl 3-(sec-butylcarbamoyl)acrylate from the above reaction at roomtemperature was added the 6-amino-1-hexanol (13.7 g, 117 mmol) and theresulting mixture was stirred overnight to give the desired product.

General Preparation Procedure for Compound (LXVI):

A solution of fumaroyl chloride in 300 mL of anhydrous THF was addedunder nitrogen and at 0° C. slowly over a one-hour period to a solutionof 1,4-Cyclohexanedimethanol in 300 mL of anhydrous THF, using a 5:1molar excess of the diol. (Note: The diol has to be used in excess,otherwise one sees over-addition of the fumaroyl chloride). After theaddition was completed, the solution was kept at 0° C. for one hour andafterwards was allowed to stir at room temperature overnight.

Excess diol was difficult to remove from the reaction product during theaqueous work-up. Therefore the reaction mixture as such was subsequentlytreated with secbutyl amine (slight excess with respect to the originalamount of fumaroyl chloride). The amine-diol product in the productmixture with 1,4-Cyclohexanedimethanol was identified by LC/MS.

Example 1 Preparation of the Clearcoat Composition

TABLE 1 Coating Composition 1A 1B 1C Portion 1 NCO Reactive Comp. XX43.57 — — (80% in butyl acetate) NCO Reactive Comp. IX — 25.49 — NCOReactive Comp. XI — — 25.49 Butyl Acetate 14.03 18.8 18.8 Flow Additive*0.54 0.47 0.47 Portion 2 Tolonate ® HDT** 19.47 19.47 19.47 CoatingComposition 1D 1E 1F 1G Portion 1 NCO Reactive Comp. XVI 29.7 — — — NCOReactive Comp. XXI — 32.28 — — NCO Reactive Comp. XXIX — — 30.16 — (80%in butyl acetate) NCO Reactive Comp. XXXI — — — 26.91 Butyl acetate20.58 21.66 12.22 19.28 Flow additive (described 0.49 0.52 0.43 0.46above) Portion 2 Tolonate ® HDT (described 19.47 19.47 19.47 19.47above) *20% BYK 301 ® flow additive, supplied by BYK-CHEMIE in propyleneglycol monomethyl ether. **Tolonate ® HDT isocyanate trimer ofhexamethylene diisocyanate supplied by Rhodia Inc.

In the preparation of each of the above coating compositions 1A-1G,Portion 1 was charged into a mixing vessel in the order shown above andmixed and then Portion 2 was charged into the mixing vessel andthoroughly mixed with Portion 1. The calculated weight solids of each ofthe above compositions was 70%. Each of the above prepared coatingcompositions 1A-1G was applied with a doctor blade over a separatephosphated cold roll steel panel primed with a layer of PowerCron®Primer supplied by PPG, Pittsburgh, Pa., to a dry coating thickness ofabout 50 micrometers and air dried at ambient temperature conditions.With Coating Compositions 1B, 1C, 1F, 1G a second set of panels wereprepared and cured for 30 minutes at 140° C. Then the Panels were testedusing the test set forth in the following table and the test results areshown in the table.

Ex. 1A Ex. 1B Ex. 1C Ex. 1D Ex. 1E Ex. 1F Ex. 1G NCO XX IX XI XVI XXIXXIX XXXI Reactive Comp Theo. Eq. Wt. 351.1 257 257 299 325 243.3 271.4Time to Gel 129 238 8 NA 201 15 40 (min) BK 3 time 37.8 82.7 23.6 113115 16.5 40.2 (min) BK 4 time 111 111 44.9 220 276 47.2 56.7 (min)Cotton Tack 69 <103 90 185 >240 50 20 Free time (min) Water Spot - 4 8 59 5 8.5 9 9 hrs RT MEK rubs 4 600 500 500 400 400 NA NA hrs RT SwellRatio 1 2.21 2.74 2.07 2.43 2.68 1.92 2.38 day RT Swell Ratio 7 2.192.49 2.06 2.29 2.44 1.75 2.15 day RT Swell Ratio 2.24 2.26 NA 2.24 2.261.67 2.00 30 day RT Persoz 139 93 53 204 190 38 30 Hardness 4 hrs RTFischer 71.2 113.2 24.5 105 118 32 14.7 Hardness 1 day RT Fischer 116135.5 125 109 129 128 104 Hardness 30 days RT Gel Fraction 93.39 96.20NA 93.42 95.83 95.11 95.21 30 days RT Swell Ratio NA Brittle, Brittle NANA 1.89 2.50 30 min 140° C. poor cure poor cure Gel Fraction NA Brittle,Brittle, NA NA 96.36 93.30 30 min 140° C. poor cure poor cure Fischer NA20.9 152 NA NA 171 127 Hardness 30 min 140° C. MEK Rubs 30 NA 10 100 NANA NA NA min 140° C. MEK Rubs 10 Na 700 100 NA NA NA NA day RT MEK Rubs10 NA 45 60 NA NA NA NA day RT plus 30 min 140° C. Infra red film cure*30 days RT NA Significant Significant NA NA Significant Significantabsorption absorption absorption absorption 30 min 140° C. NASignificantly Significantly NA NA Significant Significant less lessabsorption absorption absorption absorption 30 days RT NA SignificantlySignificantly NA NA Significant Significant plus 30 min less lessabsorption absorption 140° C. absorption absorption *Infra red filmcure - urea peaks at 1625 cm-1 & 1530 cm-1 Theo. Eq. Wt. - theoreticalequivalent weight NA-not available Rt-room temperature

The above results show that coatings made from the isocyanate-reactivecomponents of this invention have excellent early cure at roomtemperature conditions, as is evident from the short BK dry times, goodto excellent early water spot, good to excellent MEK rubs, hardness at 4hours, and good 1 day swell ratio. These coatings remain fluid for auseful period of time, and in some instances, such as, in examples 1A,1B and 1E, for extended periods of time. The films also have excellentfinal properties, such as, hardness and gel fraction.

Some the coatings of this invention exhibit the ability to undergothermo-reversible crosslinking, such as, examples 1B and 1C, whileothers do not, such as, examples 1F and 1G. The data in the table showthat when coatings of examples 1B and 1C are heated above their Tg, forexample, for 30 minutes at 140° C., they lose a significant amount oftheir crosslinking. This can be seen in the table as a loss of MEKresistance when the films are either cured initially at 140° C., or iffilms are cured for 10 days at room temperature followed by subsequentlyheating the films for 30 minutes at 140° C. (MEK rubs decrease from 700to 45 in Example 1B and from 100 to 60 in Example 1C). Additionalevidence of this thermo-reversible crosslinking can be seen using InfraRed Spectroscopy. The Infra red spectra of these films cured at roomtemperature show significant peaks at 1625 and 1530 cm-1, characteristicof the urea formed upon crosslinking of the novel amines of thisinvention with Isocyanate. When these films are subjected totemperatures of 140° C. for 30 minutes, a significant decrease in theheight of the peaks at 1625 and 1530 cm-1 occurs, almost to a point ofcomplete loss of these peaks in the Infra Red spectrum.

Other coatings of this invention, particularly shown in Examples 1F and1G, do not undergo the thermo-reversible crosslinking. This can be seenin the table by looking at the film properties of these coatings whencured at room temperature and comparing this to the film propertiesafter 140 C cure. The results are similar for swell ratios, gelfractions, hardness and Infra red cure.

Example 2 Direct-to-Metal Adhesion

In the following Example, the reactive isocyanate compound XXXIV wascombined with Desmodur® 3300 at 70% weight in butyl acetate in a 30 mmvial and vortexed for 20 seconds. The coating composition was appliedwith a doctor blade (5 mil film) over A) clean, unpolished aluminum, B)clean, unpolished cold roll steel, and C) clean, unpolished galvanizedsteel. The adhesion of the coating film was measured according to theaforementioned “X-hatch” tape test after 1 day, 3 days and seven days.The results are summarized in the attached table, showing excellentadhesion (10=highest rating) for cold roll steel and galvanized steelafter one day, and excellent adhesion to aluminum after 3 days.

Compound XXXIV Day 1 Day 3 Day 7 Plates Tape used Rating Plates RatingPlates Rating A 898 1 A 10 A 10 B 898 10 B 10 B 10 C 898 10 C 10 C 10

1. A coating composition comprising a binder consisting essentially ofa. polyisocyanate crosslinking agent; b. an isocyanate-reactivecomponent having at least one compound having the following formula:

wherein R is a hydrocarbon radical selected from a C₁ to C₂₀ linear orbranched alkyl group, or a C₅ to C₁₆ cycloaliphatic group or is aresidue obtained by removing n amino groups from a polyether polyaminewith m equal to 0 having a functionality of n and a number averagemolecular weight of less than 600, wherein the amino groups are attachedto primary carbon atoms and the ether groups are separated by at leasttwo carbon atoms; m equals 0 to 4 an n equals on average 1 to 4; X and Yindependently are O or NR³; R³ is equal to H, or C₁ to C₂₀ linear orbranched alkyl group, a C₅ to C₁₆ cycloaliphatic group, or R³ is equalto C₃═O if s=0, the compound is a cyclic imide; Z is selected from a C₁to C₂₀ linear or branched alkyl group, a C₅ to C₁₆ cycloaliphatic group,or an OH-group containing linear, branched or cycloaliphatic alkyl groupor Z comprises a fragment of the structure —CH₂—CHR⁴—R⁵, with R⁴ equalto H, or C₁ to C₂₀ linear or branched alkyl group, or a C₅ to C₁₆cycloaliphatic group and R⁵ equal to —CN or —C(═O)OR⁶, with R⁶ equal toH, or C₁ to C₂₀ linear or branched alkyl group, or a C₅ to C₁₆cycloaliphatic group; p and q are equal to 0 or 1, if p and q equal to1, the —NH—Z fragment can be bound to either C₁ or C₂, and mixtures ofcompounds and isomers thereof; s is equal to 0 or 1, with the provisothat s can only be 0 when p equals 1 and X═NR³ wherein R³ equals C₃═O;R² is H or independently selected from a C₁ to C₂₀ linear or branchedalkyl group, or a C₅ to C₁₆ cycloaliphatic group; R¹ is a hydrocarbonradical obtained by removing (q+r) hydrogen atoms from a C₁ to C₂₀linear or branched alkyl group, or a C₅ to C₁₆ cycloaliphatic group; andr is equal to 0 to
 4. 2. The coating composition of claim 1 wherein inFormula I, m=0, X═O, Y═O, R²═H, n=2, p=1, q=1, r=0, s=1, and Z isselected from a C₁ to C₂₀ linear or branched alkyl group, or a C₅ to C₁₆cycloaliphatic group.
 3. The coating composition of claim 1 wherein inFormula I, m=0, n=2, X═NH, Y═O, R²═H, p=1, q=1, r=0, s=1, and Z isselected from a C₁ to C₂₀ linear or branched alkyl group, or a C₅ to C₁₆cycloaliphatic group.
 4. The coating composition of claim 1 wherein inFormula I, m=0, n=2, X═NR³, R²═H, p=1, q=0, s=0, wherein R³ equals C₃═O,and Z is selected from a C₁ to C₂₀ linear or branched alkyl group, or aC₅ to C₁₆ cycloaliphatic group.
 5. The coating composition of claim 4wherein the isocyanate reactive component comprises


6. The coating composition of claim 1 wherein in Formula 1, m=0, n=2,X═NR³, Y═O, p=1, q=0, r=0, s=1, R³ is an alkyl group, and Z is selectedfrom a C₁ to C₂₀ linear or branched alkyl group, or a C₅ to C₁₆cycloaliphatic group.
 7. The coating composition of claim 1 wherein inFormula I, m=0, n=2, X═O, p=0, q=0, r=0, s=1, Z is selected from a C₁ toC₂₀ linear or branched alkyl group, or a C₅ to C₁₆ cycloaliphatic group,or Z comprises a fragment of the structure —CH₂—CHR⁴—R⁵, with R⁴ equalto H, or C₁ to C₂₀ linear or branched alkyl group, or a C₅ to C₁₆cycloaliphatic group and R⁵ equal to —CN or C(═O)OR⁶, with R⁶ equal toH, or C₁ to C₂₀ linear or branched alkyl group, or a C₅ to C₁₆cycloaliphatic group.
 8. The coating composition of claim 7 wherein theisocyanate reactive component is selected from the group of


9. The coating composition of claim 1 wherein in Formula I, m=1, n=1,X═O, p=0, q=0, r=0, s=1, Z is selected from a C₁ to C₂₀ linear orbranched alkyl group, or a C₅ to C₁₆ cycloaliphatic group, or Zcomprises a fragment of the structure —CH₂—CHR⁴—R⁵, with R⁴ equal to H,or C₁ to C₂₀ linear or branched alkyl group, or a C₅ to C₁₆cycloaliphatic group and R⁵ equal to —CN or C(═O)OR⁶, with R⁶ equal toH, or C₁ to C₂₀ linear or branched alkyl group, or a C₅ to C₁₆cycloaliphatic group.
 10. The coating composition of claim 9 wherein theisocyanate reactive component is selected from the group of


11. The coating composition of claim 1 wherein in Formula I, m=1, n=1,X═O, Y═O, p=1, q=1, r=0, s=1, and Z is selected from a C₁ to C₂₀ linearor branched alkyl group, or a C₅ to C₁₆ cycloaliphatic group.
 12. Thecoating composition of claim 1 wherein in Formula I, m=0, n=1, X═O,Y═NR³, p=1, q=1, r=0, s=1, Z is an OH-group containing linear, branchedor cycloaliphatic alkyl group.
 13. The coating composition of claim 1wherein in Formula I, m=1, n=1, X═O, Y═O, p=1, q=1, r=1, s=1, wherein Zis selected from a C₁ to C₂₀ linear or branched alkyl group, or a C₅ toC₁₆ cycloaliphatic group.
 14. The coating composition of claim 13wherein the isocyanate reactive component comprises


15. The coating composition of claim 1 optionally containing a polymericcomponent having a number average molecular weight of 5,000 to 50,000and having reactive groups that crosslink with an isocyanate, where thereactive groups are selected from the group consisting of hydroxyl,carboxyl, glycidyl, amine and any mixtures thereof.
 16. The coatingcomposition of claim 1 optionally containing an oligomeric componenthaving a number average molecular weight of 300 to 3,000 having reactivegroups that crosslink with an isocyanate, where the reactive groups arehydroxyl, carboxyl, glycidyl, amine, aldimines, phosphoric acid,ketimine and any mixtures thereof.
 17. The coating composition of claim1 wherein the binder contains 1 to 60% by weight, based on the weight ofthe binder, of an acrylic polymer having a number average molecularweight of 5,000 to 50,000 and having groups reactive with isocyanate.18. The coating composition of claim 17 wherein the acrylic polymerconsists essentially of polymerized monomers selected from the groupconsisting of linear alkyl (meth)acrylates having 1 to 12 carbon atomsin the alkyl group, cyclic or branched alkyl (meth)acrylates having 3 to12 carbon atoms in the alkyl group, isobornyl (meth)acrylate, styrene,alpha methyl styrene, vinyl toluene, (meth)acrylonitrile, (meth)acrylamides, and polymerized monomers that provide groups reactive withisocyanate selected from the group consisting of hydroxy alkyl(meth)acrylates, glycidyl (meth)acrylates, amino alkyl(meth)acrylatesand (meth)acrylic acid.
 19. The coating composition of claim 17 whereinthe acrylic polymer has a hydroxyl equivalent weight of 300 to 1300 andconsists essentially of polymerized monomers selected from the groupconsisting of alkyl (meth)acrylates having 1 to 12 carbon atoms in thealkyl group, cyclic or branched alkyl (meth)acrylates having 3 to 12carbon atoms in the alkyl group, isobornyl methacrylate, styrene, alphamethyl styrene, (meth)acrylonitrile, (meth)acryl amides, and polymerizedmonomers consisting of hydroxy alkyl (meth)acrylates having 1 to 4carbon atoms in the alkyl group.
 20. The coating composition of claim 1wherein the binder contains 1 to 60% by weight, based on the weight ofthe binder, of an acrylic oligomer having a number average molecularweight of 300 to 3,000 and having groups reactive with isocyanateselected from the group consisting of hydroxyl, carboxyl, glycidyl,amine, aldimines, phosphoric acid, ketimine and any mixtures thereof.21. The coating composition of claim 20 wherein the oligomer consistsessentially of polymerized monomers selected from the group consistingof linear alkyl (meth)acrylates having 1 to 12 carbon atoms in the alkylgroup, cyclic or branched alkyl (meth)acrylates having 3 to 12 carbonatoms in the alkyl group, isobornyl (meth)acrylate, styrene, alphamethyl styrene, vinyl toluene, (metha)crylonitrile, (meth)acryl amides,and polymerized monomers that provide groups reactive with isocyanateselected from the group consisting of hydroxy alkyl (meth)acrylates,glycidyl (meth)acrylates, amino alkyl(meth)acrylates and (meth)acrylicacid.
 22. The coating composition of claim 1 wherein the polyisocyanateis selected from the group consisting of aliphatic polyisocyanates,cycloaliphatic polyisocyanates, aromatic polyisocyanates and isocyanateadducts.
 23. The coating composition of claim 22 in which thepolyisocyanate is selected from the group consisting of isophoronediisocyanate, hexamethylene diisocyanate, trimer of hexamethylenediisocyanate and trimer of isophorone diisocyanate and any mixturethereof.
 24. The coating composition of claim 1 wherein the bindercontains 1 to 60% by weight, based on the weight of the binder, of apolyester having hydroxyl groups.
 25. The coating composition of claim 1wherein the binder contains 1 to 60% by weight, based on the weight ofthe binder, of a urethane oligomer that is the reaction product of apolyisocyanate selected from the group consisting of an aliphaticpolyisocyanate and a cycloaliphatic polyisocyanate; a hydroxy functionalaliphatic carboxylic acid and a monohydric alcohol selected from thegroup consisting of aliphatic monohydric alcohol and cycloaliphaticmonohydric alcohol.
 26. The coating composition of claim 25 wherein theurethane oligomer consists essentially of the reaction product of theisocyanurate of hexane diisocyanate, cyclohexanol, dimethylol propionicacid.
 27. The coating composition of claim 1 which contains about 0.1%to 5% by weight, based on the weight of the binder, of an antioxidant.28. The coating composition of claim 27 in the antioxidant is adi-substituted phenol antioxidant.
 29. The coating composition of claim1 containing 1 to 30% by weight, based on the weight of the binder, of anon-aqueous acrylic polymer dispersion.
 30. The coating composition ofclaim 1 containing pigment in a pigment to binder weight ratio of0.1/100 to 200/100 that is useful as a mono-coat top coatingcomposition.
 31. The coating composition of claim 1 containing pigmentin a pigment to binder weight ratio of 10/100 to 300/100 that is usefulas a primer or sealer composition.
 32. A high viscosity coatingcomposition comprising a binder of component a. and component b. ofclaim 1 useful as a putty.
 33. A substrate coated with the compositionof claim
 1. 34. A substrate coated with the composition of claim 1wherein the substrate is bare metal.
 35. The coated substrate of claim34 wherein the substrate is steel or aluminum.
 36. A substrate coatedwith the composition of claim 1 wherein the substrate is galvanizedsteel.
 37. A substrate having a base coating of a pigmented coatingcomposition, which is top coated with a clear coating of the compositionof claim
 1. 38. A substrate having a multi-layer coating comprising apigmented primer coating of the composition of claim 1, a base coatingof a pigmented coating composition, and a top-coating of a clear coatingof the composition of claim
 1. 39. A process for coating an auto body orauto part which comprises applying a base coating of a pigmented coatingcomposition to a substrate; applying a top-coating of a clear coating ofthe composition of claim 1 over the base coating and curing the basecoating and top-coating to form a base coat/clear coat finish on thesubstrate.
 40. An auto body or auto part coated with the composition ofclaim
 1. 41. A two component coating composition comprising Component Acomprising a polyisocyanate crosslinking agent; and Component Bcomprising an isocyanate-reactive component having at least one compoundhaving the formula (I) of claim
 1. 42. A thermoreversible coatingcomposition comprising Component A comprising a polyisocyanatecrosslinking agent and Component B comprising isocyanate reactivecomponent selected from the group of

a single isomer or as a mixture of isomers of one of the formulas, or amixture of the above formulas.